Method of preparing a cobalt, molybdenum impregnated catalyst composite



Patented Aug. 24, 1954 METHOD OF PREPARING A COBALT, MOLYB- DEN UM IMPREGNATED CATALYST COM- POSITE Grant W. Hendricks, Compton, Calif., assignor to Union Oil Company of California, Los Angeles, Calif., a corporation of California No Drawing. Application April 16, 1949, Serial No. 88,046

The catalysts described therein were prepared by coprecipitating cobalt and molybdenum oxides in molecular combination as cobalt molybdate along with, or in the presence of, a suitable carrier such as alumina. A supported co-impregnated cobalt molybdate catalyst has been described in copending application 559,650 filed October 20, 1944, by P. G. Nahin et al., now U. S. Patent 2,486,361.

It has now been found that an improved cobaltmolybdenum catalyst supported on a suitable carrier can be prepared by a two-stage impregnation process described herein and that catalysts prepared by this new method are easier to prepare, possess superior activity and have other desirable features and properties.

It is an object of this invention to simplify the preparation of supported cobalt-molybdenumcontaining catalysts and to improve the catalytic activity of such catalysts.

It is a further object of this invention to procobalt-molybdenum-containing catalysts which method affords greater control of the final catalytic composition during the preparation and manufacture.

It is another object of this invention to provide a new supported catalyst and to provide method for the use thereof for hydrocarbon conversion processes such as desulfurization, denitrogenation, hydrogenation, hydroforming and the like.

Briefly this invention relates to the preparation of a supported cobalt-molybdenum oxide catalyst which is prepared by the impregnation of the carrier in two separate and distinct steps. A suitable adsorbent carrier, e. g. activated alumina, alumina-silica, titania or the like is first immersed in an aqueous solution of a soluble molybdenum-containing salt, such as for example, an ammoniacal ammonium molybdate solution. The impregnated carrier is drained of the excess solution, is dried and heated to a temperature suflicient to decompose or oxidize the molybdenumcontaining salt to form molybdic oxide. Th carrier supporting the molybdic oxide is thereafter I vide a method for the preparation of supported 7 Claims. (Cl. 252-470) immersed in an aqueous solution of a soluble cobalt-containing salt such as for example aqueous cobaltou nitrate. The reimpregnated carrier is drained of the excess solution, dried, and heated to a temperature sufiicient to decompose or oxidize the cobalt-containing salt to form cobalt oxide. The resulting catalyst may be employed for various hydrocarbon conversions described hereinafter such as desulfurization, denitrogenation, hydrogenation, hydroforming and the like.

The carriers which are suitable and may be employed for distending the mixture of cobalt and molybdic oxides according to the process in this invention comprise alumina, silica, zirconia, thoria, magnesia, magnesium hydroxide, titania or any combination of these. The preferred carrier is activated, gel-typ alumina and particularly alumina gel containin about 3 to 8% of silica. The presence of the small amount of silica in the alumina serves to stabilize the resulting catalyst and prolongs the catalyst life as is described in U. S. Patent 2,437,532 to H. O. Huffman.

The carrier is normally shaped into the physical form desired for the catalyst prior to the impregnation steps. For this purpose the dried carrier is usually ground, mixed with a lubricant such as graphite or hydrogenated vegetable oil, and pilled. In the activation of the carrier the lubricant is removed by combustion. Alternatively the carrier may be used in. granular form or ground into powder and extruded. Where the catalyst is to be employed in a fluidized process, such as in fluidized desulfurization, denitrogenation, and the like, the carrier is formed into a finely-divided state or is ground into a finestate and is thereafter impregnated. In the case of fluidized processes the carrier can be impregnated in larger form, e. g. granules, pills, etc, and thereafter ground to the desired powder size for the processing.

The molybdenum-containing impregnation solution is preferably ammoniacal ammonium molybdate although aqueous solutions of other soluble molybdenum compounds may be employed. In the preferred method, ammonium paramolybdate is dissolved in about 14% aqueous ammonia and the resulting mixture is diluted with distilled water or with more diluted aqueous ammonia to form a clear ammonium molybdate solution of the desired concentration. The concentration of the ammonium molybdate solution will depend on the particular carrier bein employed and on the desired concentration of molybdenum in the finished catalyst. Where alumina or aluminasilica carriers are employed, and a finished catalyst. comprising between about 6 to 16% of M003- is desired, the molybdenum-containing impregnation solutions will have a concentration of molybdenum ranging from about 12 to 32 g. of MOOs/ 100 ml.

The cobalt-containing impregnation solution is preferably an aqueous solution of cobaltous nitrate although other water-soluble compounds of cobalt may be employed. Thus cobalt chloride and cobalt sulfate may be employed in the impregnation solutions although these compounds are more diificultly decomposable to active forms and require both heat and oxidation to complete their conversion to the oxide. The concentration of the cobalt-containing impregnation solution will depend upon the carrier being employed and the desired concentration of cobalt in the finished catalyst. Where alumina or aluminasilica carriers are employed and where a final catalyst composition containing from about 2 to by weight of C00 is desired, the concentration of the cobalt impregnation solution will range from about 4 to 23 g. of COO/100 ml.

In the preparation of the catalyst the carrier is first activated by heating in order to render it sufficiently adsorbent to be impregnated. Such activation may for example be effected by heating for 2 to 6 hours at 500 to 600 C. The carrier is then cooled and immersed in the molybdenumcontaining impregnation solution of the type described hereinbefore. The impregnation solution is absorbed by th carrier and the excess impregnation solution is thereafter removed. The impregnated carrier is drained and dried in a low temperature oven to remove the bulk of the water. Following the drying at, for example, 90 to 110 C. the mixture is activated by heating it to a temperature of, for example, 500 to 600 C. for two to six hours in order to decompose the molybdenum salt to M003.

The carrier supporting the molybdic oxide is then cooled and immersed in the cobalt-containing impregnation solution of the type described hereinbefore, to absorb the cobalt-containing solution. The excess solution is again removed and the impregnated material is drained and dried at low temperature for example 90 to 110 C. The material is again activated by heating at 500 to 600 C. for two to six hours in order to decompose the cobalt-containing compound to cobalt oxide. The finished catalyst prepared by this method is usually reduced in the presence of hydrogen at a temperature between 700 and 1100 F. prior to its use.

The finished catalyst is useful for effecting various hydrocarbon conversion reactions such as desulfurization, denitrogenation, hydrogenation, hydroforming, reforming, cracking, destructive hydrogenation and the like. During usage varying amounts of deposits comprising mostly carbon, nitrogen and sulfur compounds accumulate on the catalyst and are periodically removed by regeneration. Regeneration is effected by passing air diluted with flue gas, steam, nitrogen or other inert gas over the catalyst to combust the deposits while maintaining the temperature of the catalyst between 800 and 1050" F. The combustion is completed in the presence of undiluted air while maintaining the temperature of the catalyst between 800 and 1050 F. The regenerated catalyst after reduction with hydrogen has practically the same catalytic activity as the freshly prepared catalyst even after a; large number of regenerations.

For the purpose of desulfurizing petroleum stocks, shale distillates and the like, the catalyst of this invention is employed under the following conditions: reaction temperatures between about 600 to 1000 F., pressures between about atmospheric to 5000 lbs. per sq. in. or more and at space velocities between about 0.2 and 10.0 volumes of liquid feed stock per volume of catalyst per hour, and 500 to 10,000 cu. ft. of added hydrogen per barrel of feed. The particular set of conditions is determined by the stock to be desulfurized and by the nature of the product desired.

The catalyst in this invention can also be employed for denitrogenation of such stocks as coal tar distillates, shale oils and heavy petroleum distillates whereby up to 99% of the nitrogen and substantially 100% of the sulfur can be removed simultaneously. For denitrogenation of such stocks the following conditions are employed: reaction temperatures between about 700 and 1000 F., pressures between about 500 and 10,000 lbs. per sq. in., feed rates between about 0.2 and 10.0 volumes of liquid feed stock per volume of catalyst per hour, and about 1,000 to 10,000 cu. ft. of added hydrogen per barrel of feed. For the removal of nitrogen it is generally desirable to employ a two-stage denitrogenation process wherein the ammonia synthesized in the first stage is removed from the first-stage product prior to its entry into the second stage denitrogenation and wherein the ammonia and hydrogen sulfide are removed from the recycle hydrogen gas streams in each stage. Under these conditions the maximum eficiency for removing nitrogen from the stocks is obtained. The catalyst of this invention may also be employed for the process generally termed hydroforming, which process serves to reform a gasoline range hydrocarbon stock and increase its aromatic content. For processing stocks for the purpose of reforming and increasing their aromaticity, the following conditions are employed: reaction temperatures between about 800 to 1200 R, pressures between about 50 to 1000 lbs. per sq. in., space velocities between about 0.2 and 4.0 volumes of liquid feed stock per volume of catalyst per hour, and about 1,000 to 10,000 cu. ft. of added hydrogen per barrel of feed. The specific conditions are determined by the nature of the specific feed stock employed and th quality of the product desired.

Although other compositions can be prepared by the method of this invention catalyst containing from about '7 to 22% by weight and preferably from about 10 to 16% by weight of cobalt plus molybdenum oxides are employed. It is preferable that the molecular ratio of cobalt oxide to molybdic oxide (Coo/M003) be between about 0.2 and 5.0 for best results. Within these limits th preferred catalysts will contain between about 2 to 15% by weight of M003 and between about 12 to 0.5% by weight of C00.

Perhaps the process of this invention is best illustrated by the following specific examples.

EXAMPLE I An alumina-silica gel containing an estimated 95% A1203 and 5% $102 was prepared by the coprecipitation of an aqueous mixture of sodium aluminate and sodium silicate with carbon dioxide. The precipitate was washed until substantially free of sodium ions, dried at -110 C. and activated by heating for two hours at 600 C. A solution of ammonium molybdate was prepared by dissolving about 1700 parts by weight of ammonium paramolybdate, assaying about 81% by weight of M003, in about 1940 parts byweight of 28% aqueous ammonia and about 1550 parts by weight of distilled water. About 4400 parts by weight of the activated gel were immersed in the The data shown in Table 1 show the high quality product obtained by two-pass processing for the removal of nitrogen. Considering columns A, C and D, it isapparent that where a catalyst ammoniacal solution of ammonium molybdate, 5 is employed with a feed rate of 0.5 volume of feed drained, dried and heated at 600 C. for about stock per volume of catalyst a product containtwo hours. An aqueous solution of cobalt niing 0.35% nitrogen can be obtained from a feed trate was prepared by dissolving about 2150 parts stock containing 1.72% nitrogen, If, however, by weight of cobalt nitrate heXa-hydrate in about the same volume of catalyst be divided into two 2000 parts by weight of water. The carrier supequal portions and the same feed stock be deporting the molybdic oxide was then immersed nitrogenated in two stages, first over the first in the cobalt nitrate solution, drained, dried and portion of catalyst and second over the second activated by heating to 600 C. for two hours. portion of catalyst with intervening cooling of The catalyst prepared by this method contained the product and washing to separate ammonia about 9.1% M003 and 4.4% C00; the atomic and hydrogen sulfide therefrom and with the use ratio of Co/Mo was 0.93. of uncontaminated hydrogen in the second stage, At the beginning of a run the catalyst was rea product containing only 0.11% nitrogen can duced at atmospheric pressure with hydrogen thereby be obtained. while controlling the rate to maintain the tem- It is also apparent that a product containing perature below 1050 F. after which time reduconly 0.07% nitrogen by weight can be obtained tion was completed under pressure, such as at from a feed stock containing 1.72% nitrogen by the reaction pressure to be employed. While first processing the feed stock at a 0.5 v./v. and continuing the hydrogen fiow through the catasubsequently processing the first-pass product in lyst the preheated feed stock was started through a second stage operated at a 1.0 v./v. the catalyst bed and continued at the desired Excellent sulfur removal is shown for the firstfeed rate measured in terms of volumes of liquid Dass product while second-pass processing is necfeed stock per volume of catalyst per hour (also essary i orde to reduce the nitrogen to a correreferred to herein as v./v.) and for the desired spondin ly 10W fi re- 1 number of hours, after which time the hydrogen addition was continued for a short while in order EXAMPLE II to P e h catalyst of products- When titania gel is substituted for the alumi- The liquid product was cooled under pressu na-silica gel in the catalyst preparation and wlthdr awn and Washed Wlth both caustlc and processing described in Example I, substantially Water In Greer to remove any hydrogen Sulfide r the same favorable results are obtained. and ammonia. The washed anddried product was thereafter employed as a feed stock for con- EXAMPLE III 33 3 2z gfigg gig gfigg reduced A series of three cobalt molybdate catalysts Employing the aforedescribed procedure a suppptted. on alumina .Were prgpared by the series of three double-pass runs Were made with 40 preclpltatmn i dlsclosed m the Byrns an educted shale oil distillate having the followem cited herembefore' A fourth cobalt molyb' mg characteristics, date catalyst was prepared by the co-impregnation method described in copending application Gravity, t 0 F 27.2 of Nahin et al. cited hereinbefore. The four Nitrogen, W ht pe c t 1.72 catalysts were then employed for desulfurizing Sulfur, weight percent 0.74 a gas oil distillate from a Santa Maria Valley All of the runs were made Witha hydrogen pres (California) crude oil. In each instance the sure of 1100 pounds per square inch gage and at catalyst wasfirst reduced and then employed for a catalyst bed temperature of about 770 F. The the desulfunzstmn for t operatlpig cycle of six added hydrogen was varied from 3.7 to 4.0 thou- 5 hours under the following condltlons: sand cubic feet per barrel of feed. In each case perature of about 705 2 apressure of 9 pounds fresh nonqecycled, once thr0ugh hydrogen was per sq. in., space velocity of 1.0 and with 3000 employed. The data obtained are presented in of added fresh hydrogen per barrel of accompanying Table 1 wherein column A repre feed. In each case the product of the reaction sents data for a first-pass run and column B repwas cooled, washed with caustic to remQVe resents t data obtained by Secondmassing the drogen sulfide, washed with distilled water and product obtained in column A. Columns D and Subsequently dried- T f ur products were then F similarly represent the second-pass data for a y d fo ul u The data obtained from first-pass runs reported in columns C and E, rethis series of four runs appear in accompanying spectively. 0 Table 2.

Table 1 Column A B o D F Pass 1st 2nd 1st 2nd 1st 2nd Conditions of Run:

Catalyst Temp., F 770 7 770 770 770 Pressure, lbJsq. 1n.g 1,100 1,100 1,100 1,100 1,100 1,100 Added Hydrogen, MCF/bbl. of

.feed 4.0 3.7 4.0 as as as Run Length, hrs 24 6 12 6 6 6 Vol. feed/v01. catalyst/hour 0.5 1.0 1.0 1.0 2.0 1.0 Product Analysis:

Nitrogen, Wt. Percent 0. s5 0. 07 0.56 0.11 0.80 0. 22 Sulfur, Wt. Percent 0.06 0.02 0.09 0.04 0.13 0. 04 Carbon on Catalyst, Wt. Percent 5. 55 2.51 5.08 3.12 4. 91 3.15 Hydrogen Consumption, cu. ftJbbl.

of feed 05o nil 850 ml 650 (30) Table 2 Method of Preparation. Byrns Byrns Byrns Nahin Composition of Catalyst:

C00, weight percent l3. 1 7. l 5. 7 4. 9

M;\, weight percent l2. 2 4. 5 2. 9 7. 4

COO-i-MOOa, weight percent. 25.3 11.6 8.6 12.3 Sulfur in Product, weight percent 0. 0. 23 0. 29 0. 09

EXAMPLE IV In this example a series of five impregnated catalysts were prepared by three different impregnation procedures. Catalyst 1 and 2- were co-impregnated catalysts prepared according to the method described by Nahin et al. in the copending application previously cited.

In the preparation of catalyst 1 an ammonical ammonium molybdate solution was prepared by dissolving 104 parts by weight of ammonium pararnolybdate in a. mixture of 190 parts by weight of 28% aqueous ammonia and 123 parts by weight of distilled water. A cobalt-containing solution was prepared by dissolving 155 parts by weight of cobaltous nitrate hexahydrate in 65 parts by weight of distilled water. The cobalt-containing solution was added slowly and dropwise into the molybdenum solution while rapidly stirring the molybdenum solution. A coprecipitated carrier containing about 95% by weight of alumina and about 5% by weight of silica was activated by heating for six hours at 600 C. About 420 parts by weight of the activated carrier were immersed in the mixed solution for one hour, drainedof the excess solution, dried overnight at 90 to 110 C. and finally heated for two hours at 600 C.

Catalyst 2 was prepared in substantially the same mamier as catalyst 1 using a slightly difierent impregnation solution.

Catalysts 3, 4 and 5 were prepared by separately impregnating cobalt and molybdenum in the excess solution, dried and activated by heating for two hours at 600 0.

Catalyst 4 was prepared as follows: about 420 parts by weight of the activated alumina-silica carrier were immersed in an ammoniacal ammonium molybdate solution prepared by dissolving about 104 parts by weight of ammonium paramolybdate in a mixture of about 225 parts by weight of 28% aqueous ammonium hydroxide and about 233 parts by Weight of distilled water. The impregnated carrier was drained of the excess solution, dried and calcined for two hours at 600 C. The carrier supporting the molybdic oxide was thereafter immersed in an aqueous solution of cobaltous nitrate prepared by dissolving about 155 parts by weight of cobaltous nitrate hexahydrate in about 390 parts by weight of distilled water. The impregnated carrier was drained of the excess solution, dried and activated by heating for two hours at 600 C.

Catalyst 5 was prepared in the same manner as catalyst 4 with the exception that the concentration of each of the two solutions was changed to give a difierent catalyst composition.

The five catalysts were separately reduced and each was employed for desulfurizing of a straight run gas oil distillate from a Santa Maria Valley crude oil similar to that described in Example III. The gas oil feed stock contained 2.33% by weight of sulfur and had a 33.2 A. P. I. gravity. The following operating conditions were employed for the desulfurization: a reaction temperature of about 750 R, a space velocity of 2.0 volumes of feed stock per volume of catalyst per hour, a pressure of 150 pounds per sq. in. gage, an operating cycle of six hours and 3000 cu. ft. of added hydrogen per barrel of feed. The products from each of the runs was processed in the manner described in Example I. The data obtained therefrom are shown in accompanying Table 3.

Table 3 Catalyst number 7 Method of impregnation Composition:

M003 weight percent 000, Weight percent C0O+M0Oa Examination of product:

Liquid recovery. volume percent Sulfur in product, weight percent Acid solubility, volume percent Olefins, volume percent l 1 l 2 i 3 4 5 Cod-Mo". Co+M0 Co first, M0 M0 first, 00 Mo first, 00

second. second. second.

two impregnation stages with the cobalt being The impregnated carrier was drained, dried and calcined for two hours at 600 C. The carrier supporting the cobalt oxide was then immersed in an ammoniacal ammonium molybdate 50111-1 tion prepared by dissolving 104 parts by weight of ammonium paramolybdate in a mixture of about 225 parts by weight of 28% aqueous ammonia and about 208 parts by weight of distilled water. The impregnated mixture was drained of It is apparentthat highly active desulfurization catalysts are prepared by impregnating the carrier in two separate stages wherein the molybdenum is deposited in the first impregnation stage and cobalt is deposited in the second. The two-stage impregnated catalysts, wherein the M003 is deposited first and the C00 second, are superior to the single stage coimpregnated catalysts in that they give a higher yield liquid prodnot which are also somewhat richer in aromatics as determined by substracting the olefin content from the acid soluble content. A comparison of catalyst 3 with 4 and 5 shows that better desulfurization is obtained if the M063 is deposited first, rather than the C00 first, in the two-stage process.

EXAMPLE V Catalysts 2, 3 and 5 prepared as described in Example III were also tested for the hydroforming of a naphthene-rich straight run distillate having an A. P. I. gravity of 52.7 and containing about 12.7 volume per cent aromatics. The following conditions were employed: A process to claim 1 wherein said carrier is first impregnated with an aqueous solution of a cobalt compound, and is thereafter impregnated with an aqueous solution of a molybdenum compound.

period of four hours, a space velocity of 1.0 3. A method of preparing a catalyst according volumes of feed stock per volume of catalyst per to claim 1 wherein said carrier is first impreghour. a pressure of 100 pounds, an isothermal nated with an aqueous solution of a molybdenum block temperature of 950 F. (temperature of compound, and is thereafter impregnated with large steel block surrounding the reactor tube) an aqueous solution of a cobalt compound. and 3000 cu. ft. of fresh added hydrogen per 4. A method according to claim 1 wherein the barrel of feed. The products of the runs were carrier is an alumina gel. analyzed for aromatic content and the amount 5. A method according to claim 1 wherein of synthetic aromatics was calculated by assumthe carrier is an alumina-silica gel. ing that the aromatics originally present in the 6. A method according to claim 1 wherein the feed stock passed through the reactor unchanged 5 carrier is a it nia eland were completely recovered in the products. '7. A method for preparing a catalyst consist- The hydroforming data for synthetic aromatics ing essentially of a minor proportion of cobalt are shown in accompanying Table 4, oxide plus molybdenum oxide and a major pro- Table 4 Catalyst number 2 3 5 Method ot'impregnation Co+Mo Co first, M0 M0 first, 00

second. second. Composition:

000, Weight percent 9. 4 9. 6 l0. 1 M003, weight percent 5. 5 4. 5 3. 8 C0O+M0Oa, weight percent 14. 9 14.1 13.9 Synthetic aromatics, volume percent feed 30. 2 31. 1 34- 5 The foregoing disclosure of my invention is portion of a carrier which comprises immersing not to be considered as limiting since many varian adsorbent alumina gel containing between ations may be made by those skilled in the art about 3 and 8% by weight of silica in an aqueous without departing from the scope or spirit of ammoniacal ammonium molybdate solution to the following claims: 35 form a molybdenum-impregnated gel, drying said I claim: molybdenum-impregnated gel, activating said 1. A method of preparing a catalyst consisting molybdenum-impre n t ge y heating, essentially of a minor proportion of cobalt oxide mersing a d p at gel in an qu u S0 11- plus molybdenum oxide and a major proportion tion of cobaltous nitrate to form a cobalt-imof a carrier which comprises impregnating an pregnated gel, drying said cobalt-impregnated e adsorbent carrier with an aqueous solution of a and activating Said Cobalt-impregnated lcom ound of one meta select (1 from the class consisting of cobalt i molyebdenum, decom References Cited in the file of this patent posing said compound during heating to form UNITED STATES PATENTS the corresponding metal oxide on said carrier, Number Name Date impregnating said carrier with an aqueous solu- 2,270,165 Gran et aL Jan 13 1942 tion of a compound of the other of said metals 2,296,406 Spicer et aL Sept 22, 1942 and decomposmg sa1d compound during heating 2,393,238 Byms Jan. 22, 1946 to form the corresponding metal oxide of said 2,411,329 Hufi'm 26, 1946 other metal. 2,486,361 Nahin et a1. Oct. 25, 1949 A method of preparing a catalyst according 2,499,255 Parker 28, 1950 

1. A METHOD OF PREPARING A CATALYST CONSISTING ESSENTIALLY OF A MINOR PROPORTION OF COBALT OXIDE PLUS MOLYBDENUM OXIDE AND A MAJOR PROPORTION OF A CARRIER WHICH COMPRISES IMPREGNANTING AN ADSORBENT CARRIER WITH AN AQUEOUS SOLUTION OF A COMPOUND OF ONE METAL SELECTED FROM THE CLASS CONSISTING OF COBALT AND MOLYBDENUM, DECOMPOSING SAID COMPOUND DURING HEATING TO FORM POSING SAID COMPOUND DURING HEATING TO FORM IMPREGNATING SAID CARRIER WITH AN AQUEOUS SOLUTION OF A COMPOUND OF THE OTHER OF SAID METALS AND DECOMPOSING SAID COMPOUND DURING HEATING TO FORM THE CORRESPONDING METAL OXIDE OF SAID OTHER METAL. 